Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
  • G03C7/302—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

• the invention relates to a color photographic silver halide material which is characterized on the one hand by a low application of silver halide and on the other hand by certain silver halide emulsions. Furthermore, the invention relates to a development process for the above-mentioned material, in which a combined action of developer and H2O2 is carried out.
• Conventional silver halide materials for the production of color control formers each contain a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a reflective support, to which yellow couplers, magenta couplers and cyan couplers are assigned in the order given. These materials also contain common intermediate and protective layers.
• certain minimum amounts of silver halides are required, which on the other hand also ensure sufficient sensitivity during the copying process. Amounts of silver halide, given as AgNO3, of at least 1 g / m2 are currently in use across all 3 color densities.
• the development creates a corresponding silver image, which has to be removed in order to make the colors appear clear and bright. This occurs in the silver removal stage following the development, which consists of the bleaching and fixing steps.
• the processing process is completed by watering or stabilizing and drying.
• silver chloride bromide emulsions with at least 30 mol% bromide and silver bromide iodide emulsion with high bromide contents were used. 100% silver chloride emulsions were also proposed, but did not produce sufficient results when reworked.
• the object of the present invention was to find such a reinforcement method and a suitable material with which images of sufficient quality can be obtained simply and reliably.
• the invention relates to a color photographic recording material with at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler as well as usual intermediate and protective layers, characterized in that the silver halide is applied all light-sensitive layers, indicated as AgNO3, is 0.5 to 0.2 g / m2 and in at least one light-sensitive layer, a silver chloride bromide emulsion with 0.1 to 3 mol% of silver bromide is used as the emulsion. Preferably there is at least 50%.
• Such emulsions are obtained in particular by treating AgCl emulsions and AgClBr emulsions with a lower bromide content than desired after sensitization with the aqueous solution of a bromide.
• the emulsions of all the light-sensitive layers are preferably AgClBr emulsions of the type mentioned, it being possible for the bromide fractions to differ from layer to layer within the inserted frame.
• the silver halides preferably have a bromide content of 0.2-2 mol%.
• the silver halide grains can contain up to 0.5 mol% of silver iodide, but are preferably free of silver iodide.
• the color photographic recording material preferably consists of a reflective support, on which, in the order given, a layer sensitive to blue, containing at least one yellow coupler, a layer sensitive to green, to some extent containing a purple coupler, and a layer sensitive to red, containing at least one cyan coupler, and customary intermediate and protective layers are applied .
• Another object of the invention is a development process for the above material, in which, after imagewise exposure, the material is treated with a color developer of the p-phenylenediamine series and aqueous H2O2.
• the development can take place in one or two baths, the concentrations of color developer preferably being 0.01 to 0.1 mol / l and H2O2 being 0.5 to 25 g / l.
• concentrations of color developer preferably being 0.01 to 0.1 mol / l and H2O2 being 0.5 to 25 g / l.
• the two-bath development color developer and H2O2 in separate baths is preferred.
• bleaching and fixing can be carried out in one bath (bleach-fix bath).
• a particular advantage of the process is that the small amount of silver halide produces such a weak silver image that the color image no longer interferes and therefore does not need to be removed. The bleaching can thus be omitted.
• Fixing (dissolving the unexposed silver halide) can also be omitted if the silver halide is converted into a light-insensitive silver complex salt by a stabilizing bath. In this case, the drying can immediately follow the stabilization.
• the silver halide emulsion layers essentially contain a binder, which is also a main component of the intermediate and protective layers.
• Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
• Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
• Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
• Semi-synthetic gelatin substitutes are usually modified natural products.
• Cellulose derivatives such as hydroxyalkyl cellulose, Examples of these are carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.
• the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
• functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
• the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
• the silver halides used according to the invention can be predominantly compact crystals which are, for example, regularly cubic or octahedral or can have transitional forms.
• the silver halides can also be in the form of platelet-shaped crystals whose average ratio of diameter to thickness is, for example, at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
• the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%. Homodisperse silver halide emulsions are preferred. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
• Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
• the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
• various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
• the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
• the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
• the water-soluble silver salts and the halides are brought together either one after the other by the single-jet or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
• the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
• so-called inverse precipitation with an excess of silver ions is also possible.
• the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
• Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
• the precipitation can also be carried out in the presence of sensitizing dyes.
• Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
• the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
• the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
• the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
• a reduction sensitization with the addition of reducing agents can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8) .
• the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
• Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants will.
• metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants
• Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are also suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
• mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
• the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
• the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
• the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
• non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
• cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
• sulfonium compounds or phosphonium compounds anionic surfactants, containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group
• ampholytic surfactants for example amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
• fluorine-containing surfactants which are known, for example, from GB-PS 1 330 356, 1 524 631 and US-PS 3,666,478 and 3,689,906.
• the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
• Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• Color couplers for generating the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular of the benzoylacetanilide and ⁇ -pivaloylacetanilide type. Numerous examples of the couplers are described in the literature. The couplers can also be of high molecular weight, so-called latex couplers.
• High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
• the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
• the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
• the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
• Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described, for example, in US-A-2 322 027, USA-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
• oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
• the compounds can also be introduced into the casting solution in the form of loaded latices.
• anionic water-soluble compounds e.g. dyes
• pickling polymers e.g. acrylic acid
• Suitable oil formers are, for example, alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
• oil formers examples include dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N,
• Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers.
• the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
• Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov 1979), page 650 and in EP-AO 069 070, 0 098 072, 0 124 877, 0 125 522.
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
• Compounds that absorb UV light are intended to protect the image dyes from fading due to UV-rich daylight. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
• benzotriazole compounds US-A-3 533 794
• 4-thiazolidone compounds US-A-3 314 794 and 3 352 681
• benzophenone compounds JP-A-2784/71
• cinnamic acid ester compounds US-A-3 705 805 and 3,707,375
• butadiene compounds US-A-4
• UV absorbers should absorb light up to 400 nm and have a steep drop in their light absorption capacity at wavelengths above 400 nm.
• Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
• Suitable whiteners are described, for example, in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
• binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
• photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
• the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
• the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
• suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
• Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3, 5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2
• the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to the extent that no further change in the sensitometry and the change in the crosslinking reaction is caused by the crosslinking reaction Swelling of the layer structure occurs. Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
• hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
• Suitable color developer compounds are aromatic compounds of the p-phenylondiamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl ) -3-methyl-p-phenylenediamine. Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist,
• Treatment with aqueous H2O2 can be carried out simultaneously or after development.
• an acidic stop bath or watering as well as bleaching and fixing can follow, whereby bleaching and fixing can be dispensed with, particularly because of the small amounts of silver that are formed. Fixing can be replaced by stabilization.
• Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents.
• Iron (III) complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred.
• Persulphates and peroxides for example hydrogen peroxide, are also suitable as bleaching agents.
• the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
• the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
• this stabilizing bath also functions as a final bath.
• a monodisperse silver chloride emulsion of 0.8 microns average grain diameter was prepared by double entry of an AgNO3 and NaCl solution containing Na4IrCl6.
• the Ir content was 0.05 x 10 ⁇ 6 mol / mol Ag.
• the emulsion was flocculated in the usual way, washed and redispersed with gelatin.
• the weight ratio gelatin-silver (as AgNO3) was 0.5.
• the AgCl content was 1 mol per kg of emulsion.
• the emulsion was then ripened with 20 x 10 ⁇ 6 moles of thiosulfate and 2 x 10 ⁇ 6 moles of AuCl4 per mole of Ag for optimal sensitivity.
• the emulsion was sensitized with blue sensitizer BS1 (400 x 10 ⁇ 6 mol / mol Ag) for the blue spectral range and then stabilized with stabilizer ST 1 (243 x 10 ⁇ 6 mol / mol Ag).
• EM 2 a green-sensitive emulsion with 99.5 mol%. Chloride, 0.5 mol% bromide and an average grain diameter of 0.4 microns (EM 7).
• a color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene.
• the quantities given relate to 1 m2.
• the corresponding amounts of AgNO3 are given
• Example 1 to 6 were exposed imagewise by a sensitometer and developed as follows: Since the amount of silver developed was very small, no bleaching stage was used.
• Layer structures 1-6 were repeated with the change that 0.4 mg / m 2 of 5-butylbenzotriazole were added to the blue-sensitive emulsion. These layer structures 7-12 were also exposed by a sensitometer and developed as follows:

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• 1990
  • 1990-03-22 DE DE19904009181 patent/DE4009181A1/de not_active Withdrawn
  • 1990-12-20 EP EP90124875A patent/EP0447656A1/fr not_active Withdrawn

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